Co2 adsorbent

ABSTRACT

A CO 2  adsorbent that includes MIL-100(Fe) and various amounts of carbon nanotubes that are dispersed therein, and a method of capturing CO 2  with a CO 2  adsorbent that includes an adsorbent matrix of a zeolite and/or a metal organic framework and carbon nanotubes that are dispersed within the adsorbent matrix. Various embodiments of the CO 2  adsorbent and the method of capturing CO 2  are also provided.

BACKGROUND OF THE INVENTION Technical Field

The present invention relates to a method of capturing CO₂ with a CO₂adsorbent that includes an adsorbent matrix of a zeolite and/or a metalorganic framework and carbon nanotubes dispersed in the adsorbentmatrix.

Description of the Related Art

The “background” description provided herein is for the purpose ofgenerally presenting the context of the disclosure. Work of thepresently named inventors, to the extent it is described in thisbackground section, as well as aspects of the description which may nototherwise qualify as prior art at the time of filing, are neitherexpressly or impliedly admitted as prior art against the presentinvention.

In recent years, environmental pollution is identified as one of themost significant issues with respect to environmental health and safety.The major concern is the formation of greenhouse gases, most importantlycarbon dioxide, as a result of burning fossil fuels. Continuous releaseof carbon dioxide into the atmosphere causes global warming, shorefloods, atmospheric heat waves, land droughts, and destruction ofcold-marine life, which may directly or indirectly reduce world's grossdomestic product by about 5 to 20% [Lee, S.-Y. and Park, S.-J., A reviewon solid adsorbents for carbon dioxide capture. Journal of Industrialand Engineering Chemistry, 2015, 23: p. 1-11]. The increase of theatmospheric temperature was measured to be about 0.74% in the lastcentury and is predicted to reach to about 6.4% at the end of thecurrent century [Lee, S.-Y. and Park, S.-J., A review on solidadsorbents for carbon dioxide capture. Journal of Industrial andEngineering Chemistry, 2015, 23: p. 1-11]. In view of that, asignificant effort is dedicated to minimize and control CO₂ emissionsinto the atmosphere. A switch from fossil fuel energy to apollution-free source of energy, e.g. renewable energy sources, does notappear to be practicable in a short period of time. Therefore, onepossible solution to continue to use fossil fuel energy would be tominimize CO₂ emissions into the atmosphere by carbon capture andstorage.

The on-going research in the field of Carbon Capture and Storage (CCS)is gaining momentum every day. A vast number of research studies involveCO₂ separation and storage, with the primary objective of developingnovel adsorption materials or CO₂ adsorbents [Ben-Mansour, R., Habib, M.A., Bamidele, O. E., Basha, M., Qasem, N. A. A., Peedikakkal, A., Laoui,T., and Ali M., Carbon capture by physical adsorption: Materials,experimental investigations and numerical modeling and simulations—Areview, Applied Energy, 2016, 161: p. 225-255]. Also, a number ofresearchers have studied the processes of carbon dioxide capture e.g.pressure swing adsorption and temperature swing adsorption [Biswas,Agrawal, S., and Sinha, S., Modeling and simulation for pressure swingadsorption system for hydrogen purification. Chemical and BiochemicalEngineering Quarterly, 2010, 24(4): p. 409-414; Casas, N Schell, J.,Pini, R and Mazzotti, M., Fixed bed adsorption of CO₂/H₂ mixtures onactivated carbon: experiments and modeling. Adsorption, 2012, 18(2): p.143-161; Cavenati, S Grande, C. A., and Rodrigues, A. E., Separation ofmixtures by layered pressure swing adsorption for upgrade of naturalgas, Chemical Engineering Science, 2006, 61(12): p. 3893-3906; Chaffee,A. L., Knowles, G. P., Liang, Z., Zhang, J., Xiao, P., and Webley, P.A., CO₂ capture by adsorption: Materials and process development,International Journal of Greenhouse Gas Control, 2007, 1(1): p. 11-18;Cho, S.-H., Park, J.-H., Beum, H.-T Han, S.-S., and Kim,J.-N., A 2-stagePSA process for the recovery of CO₂ from flue gas and its powerconsumption in Carbon Dioxide Utilization for Global Sustainability,Proceedings of 7th the International Conference on Carbon DioxideUtilization, 2004, Elsevier B V. p. 405-410; Choi, W.-K Kwon, T.-I.,Yeo, Y.-K., Lee, H Song, H. K., and Na, B.-K., Optimal operation of thepressure swing adsorption (PSA) process for CO₂ recovery, Korean Journalof Chemical Engineering, 2003, 20(4): p. 617-623; Dantas, T. L., Amorim,S. M., Luna, F. M. T., Silva Jr, I. J., de Azevedo, D. C., Rodrigues, A.E., and Moreira, R. F., Adsorption of carbon dioxide onto activatedcarbon and nitrogen-enriched activated carbon: surface changes,equilibrium, and modeling of fixed-bed adsorption, Separation Scienceand Technology, 2009, 45(1): p. 73-84; Dantas, T. L. P., Luna, F. M. T.,Silva, I. J., de Azevedo, D. C. S., Grande, C. A., Rodrigues, A. E., andMoreira, R. F. P. M., Carbon dioxide-nitrogen separation throughadsorption on activated carbon in a fixed bed, Chemical EngineeringJournal, 2011, 169(1-3): p. 11-19; Dantas, T. L. P., Luna, F. M. T.,Silva, I. J., Torres, A. E. B., de Azevedo, D. C. S., Rodrigues, A. E.,and Moreira, R. F. P. M., Carbon dioxide-nitrogen separation throughpressure swing adsorption, Chemical Engineering Journal, 2011, 172(2-3):p. 698-704; Gomes, V. G. and Yee, K. W. K., Pressure swing adsorptionfor carbon dioxide sequestration from exhaust gases, Separation andPurification Technology, 2002, 28(2): p. 161-171; Krishnamurthy, S.,Rao, V. R Guntuka, S., Sharratt, P., Haghpanah, R., Rajendran, A.,Amanullah, M., Kari I. A., and Farooq, S., CO₂ capture from dry flue gasby vacuum swing adsorption: A pilot plant study, AIChE Journal, 2014,60(5): p. 1830-1842; Lee, C.-H., Yang, J., and Ahn, H., Effects ofcarbon-to-zeolite ratio on layered bed H₂ PSA for coke oven gas, AIChEJournal, 1999, 45(3): p. 535-545; Park, J.-H., Kim, J.-N., and Cho,S.-H., Performance analysis of four-bed H₂ PSA process using layeredbeds, AIChE Journal, 2000, 46(4): p. 790-802; Wang, L., Liu, Z., Li,P.,Yu, J., and Rodrigues, A. E., Experimental and modeling investigation onpost-combustion carbon dioxide capture using zeolite 13X-APG by hybridVTSA process, Chemical Engineering Journal, 2012, 197: p. 151-161; Wang,L. Yang, Y., Shen, W., Kong, X., Li, P., Yu, J., and Rodrigues, A. E.,Experimental evaluation of adsorption technology for CO₂ capture fromflue gas in an existing coal-fired power plant, Chemical EngineeringScience, 2013, 101: p. 615-619]. In addition, some researchers havefocused on developing adsorbent materials with enhanced CO₂ capturecapacities and CO₂ selectivity. However, a relatively low thermalconductivity of the adsorbent materials has been shown to be a majordrawback that restricts the adsorbent materials from having enhanced CO₂capture capacities and CO₂ selectivity.

In view of the forgoing, one objective of the present disclosure is toprovide a CO₂ adsorbent that includes MIL-100(Fe) and various amounts ofcarbon nanotubes that are dispersed therein. Another objective of thepresent disclosure provides a method of capturing CO₂ with a CO₂adsorbent that includes an adsorbent matrix of a zeolite and/or a metalorganic framework and carbon nanotubes that are dispersed within theadsorbent matrix.

BRIEF SUMMARY OF THE INVENTION

According to a first aspect, the present disclosure relates to a methodof capturing CO₂, involving contacting a CO₂-containing stream with aCO₂ adsorbent to adsorb at least a portion of CO₂ from theCO₂-containing stream, wherein the CO₂ adsorbent comprises a) anadsorbent matrix comprising a zeolite and/or a metal organic framework,b) carbon nanotubes that are dispersed within the adsorbent matrix,wherein a weight percent of the carbon nanotubes in the CO₂ adsorbent isin the range of 0.01 wt % to 5.0 wt %, relative to the total weight ofthe CO₂ adsorbent.

In one embodiment, the CO₂-containing stream contains CO₂ and at leastone gaseous substance selected from the group consisting of nitrogen,oxygen, argon, helium, water vapor, hydrogen, carbon monoxide, methane,and ethane. Accordingly, a volumetric ratio of CO₂ to the at least onegaseous substance is in the range of 1:50 to 5:1.

In one embodiment, the CO₂-containing stream is contacted with the CO₂adsorbent at a temperature in the range of −20 to 100° C.

In one embodiment, the CO₂-containing stream is contacted with the CO₂adsorbent at a pressure in the range of 0.5 to 10 bars.

In one embodiment, the method further involves degassing the CO₂adsorbent in a sub-atmospheric pressure prior to the contacting.

In one embodiment, the CO₂ adsorbent is degassed in a temperature rangeof 10 to 400° C., for no more than 24 hours.

In one embodiment, the adsorbent matrix comprises a zeolite and a metalorganic framework.

In one embodiment, the adsorbent matrix comprises the metal organicframework which is selected from the group consisting of Mg-MOF-74 andMIL-100(Fe).

In one embodiment, the adsorbent matrix comprises the zeolite which iszeolite 13X.

In one embodiment, the weight percent of the carbon nanotubes in the CO₂adsorbent is in the range of 0.05 wt % to 1.5 wt %, relative to thetotal weight of the CO₂ adsorbent.

In one embodiment, the carbon nanotubes are single-walled carbonnanotubes.

In one embodiment, the carbon nanotubes are multi-walled carbonnanotubes.

In one embodiment, the carbon nanotubes are dispersed in the adsorbentmatrix without forming chemical bonds with the adsorbent matrix.

In one embodiment, the carbon nanotubes are homogenously dispersed inthe adsorbent matrix.

According to a second aspect, the present disclosure relates to a CO₂adsorbent including i) an adsorbent matrix comprising MIL-100(Fe), ii)carbon nanotubes that are dispersed within the adsorbent matrix, whereinthe carbon nanotubes are dispersed in the adsorbent matrix withoutforming chemical bonds with the adsorbent matrix.

In one embodiment, the CO₂ adsorbent has a CO₂ adsorption capacity inthe range of 0.5 to 20 mmol CO₂ per one gram of the CO₂ adsorbent, at atemperature in the range of 10 to 40° C.

In one embodiment, the CO₂ adsorbent has a thermal conductivity of up to500% higher than a thermal conductivity of a pristine adsorbent thatcomprises MIL-100(Fe) and does not include carbon nanotubes.

The foregoing paragraphs have been provided by way of generalintroduction, and are not intended to limit the scope of the followingclaims. The described embodiments, together with further advantages,will be best understood by reference to the following detaileddescription taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the disclosure and many of the attendantadvantages thereof will be readily obtained as the same becomes betterunderstood by reference to the following detailed description whenconsidered in connection with the accompanying drawings, wherein:

FIG. 1 is a schematic representation of a CO₂ capturing system.

FIG. 2 represents X-ray diffraction spectra of CO₂ adsorbents havingzeolite 13X and various amounts of carbon nanotubes.

FIG. 3 represents CO₂ adsorption isotherms of CO₂ adsorbents havingzeolite 13X and various amounts of carbon nanotubes, at a temperature of25° C.

FIG. 4 represents breakthrough curves of CO₂ adsorbents having zeolite13X and various amounts of carbon nanotubes, at a temperature of 25° C.and a pressure of 1.0 atm, wherein a CO₂-containing stream having CO₂and N2, with a CO₂:N2 volumetric ratio of 1:4, is contacted with the CO₂adsorbents.

FIG. 5 represents the CO₂ adsorption capacity (dashed bars) and thebreakpoint onset (solid bars) of CO₂ adsorbents having zeolite 13X andvarious amounts of carbon nanotubes, at a temperature of 25° C. and apressure of 1.0 atm.

FIG. 6 represents X-ray diffraction spectra of CO₂ adsorbents havingMg-MOF-74 and various amounts of carbon nanotubes.

FIG. 7 represents CO₂ adsorption isotherms of CO₂ adsorbents havingMg-MOF-74 and various amounts of carbon nanotubes, at a temperature of25° C.

FIG. 8 represents breakthrough curves of CO₂ adsorbents having Mg-MOF-74and various amounts of carbon nanotubes, at a temperature of 25° C. anda pressure of 1.0 atm, wherein a CO₂-containing stream having CO₂ andN2, with a CO₂:N2 volumetric ratio of 1:4, is contacted with the CO₂adsorbents.

FIG. 9 represents the CO₂ adsorption capacity (dashed bars) and thebreakpoint onset (solid bars) of CO₂ adsorbents having Mg-MOF-74 andvarious amounts of carbon nanotubes, at a temperature of 25° C. and apressure of 1.0 atm.

FIG. 10 represents CO₂ adsorption isotherms of CO₂ adsorbents havingMIL-100(Fe) and various amounts of carbon nanotubes, at a temperature of25° C.

FIG. 11 represents breakthrough curves of CO₂ adsorbents havingMIL-100(Fe) and various amounts of carbon nanotubes, at a temperature of25° C. and a pressure of 1.0 atm, wherein a CO₂-containing stream havingCO₂ and N2, with a CO₂:N2 volumetric ratio of 1:5.6, is contacted withthe CO₂ adsorbents.

FIG. 12 represents the CO₂ adsorption capacity (dashed bars) and thebreakpoint onset (solid bars) of CO₂ adsorbents having MIL-100(Fe) andvarious amounts of carbon nanotubes, at a temperature of 25° C. and apressure of 1.0 atm.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Referring now to the drawings, wherein like reference numerals designateidentical or corresponding parts throughout the several views.

According to a first aspect, the present disclosure relates to a methodof capturing CO₂. The method involves contacting a CO₂-containing streamwith a CO₂ adsorbent to adsorb at least a portion of CO₂ from theCO₂-containing stream, thereby forming a CO₂-depleted stream.

The term “CO₂-containing stream” as used in this disclosure refers to agaseous stream that contains carbon dioxide (CO₂), and one or moregaseous substances including, but not limited to nitrogen, oxygen,argon, helium, water vapor, hydrogen, carbon monoxide, methane, ethane,hydrogen sulfide, nitrogen oxides (i.e. nitric oxide, nitrous oxide,nitrogen dioxide), or sulfur dioxide. Preferably, a volumetricconcentration of the hydrogen sulfide, nitrogen oxides (i.e. nitricoxide, nitrous oxide, nitrogen dioxide), or sulfur dioxide, if present,is no more than 500 ppm, preferably no more than 100 ppm, and morepreferably no more than 50 ppm, relative to the total volume of theCO₂-containing stream. In a preferred embodiment, a volumetric ratio ofCO₂, which is present in the CO₂-containing stream, to the one or moregaseous substances present in the CO₂-containing stream is in the rangeof 1:50 to 5:1, preferably 1:45 to 4:1, preferably 1:40 to 3:1,preferably 1:35 to 2:1, preferably 1:30 to 1:1, preferably 1:25 to 1:2,preferably 1:20 to 1:3, preferably 1:15 to 1:4, preferably 1:10 to 1:5.

In some embodiments, the CO₂-containing stream is contacted with the CO₂adsorbent at a temperature in the range of −20 to 100° C., preferably−10 to 80° C., preferably 0 to 60° C., preferably 10 to 40° C.,preferably 20 to 30° C., preferably about 25° C. In addition, theCO₂-containing stream is contacted with the CO₂ adsorbent at a pressurein the range of 0.5 to 10 bars, preferably 0.6 to 8 bars, preferably 0.7to 6 bars, preferably 0.8 to 4 bars, preferably 0.9 to 2 bars,preferably about 1 bar.

The CO₂-containing stream may be recovered (or may be directly supplied)from an upstream processing unit, e.g. a methanol producing unit, asteam power plant, a steam generator, a combustor, an oxy-fuelcombustor, an ion transport membrane, etc. In view of that, incircumstances where the temperature or the pressure of theCO₂-containing stream falls outside of the above mentioned operatingtemperature and pressure ranges, the temperature and the pressure of theCO₂-containing stream may be adjusted to be within said operatingtemperature and pressure ranges prior to contacting the CO₂-containingstream with the CO₂ adsorbent.

The tern “CO₂-depleted stream” as used herein refers to a gaseous streamthat is formed after CO₂ is adsorbed onto the CO₂ adsorbent. Acomposition of the CO₂-depleted stream may vary depending on thecomposition of the CO₂-containing stream. In some embodiments, theCO₂-depleted stream includes CO₂ and one or more gaseous substancesincluding, but not limited to nitrogen, oxygen, argon, helium, watervapor, hydrogen, carbon monoxide, methane, ethane, hydrogen sulfide,nitrogen oxides (i.e. nitric oxide, nitrous oxide, nitrogen dioxide), orsulfur dioxide. Accordingly, a volumetric ratio of CO₂, which is presentin the CO₂-depleted stream, to the one or more gaseous substances mayvary in the range of 1:100 to 1:1, preferably 1:98 to 1:5, preferably1:95 to 1:10, preferably 1:90 to 1:15, preferably 1:85 to 1:20,preferably 1:80 to 1:25, preferably 1:75 to 1:30. In another preferredembodiment, the CO₂-depleted stream does not include CO₂. In anotherembodiment, the CO2-depleted stream is substantially free of CO₂, andaccordingly, it contains less than 100 ppm, preferably less than 10 ppm,preferably less than 1 ppm, preferably less than 1 ppb CO₂.

The CO₂-containing stream may be contacted with the CO₂ adsorbent bypassing the CO₂-containing stream over the CO₂ adsorbent. Alternatively,the CO₂-containing stream may stay stagnant over the CO₂ adsorbent, i.e.as an atmosphere to the CO₂ adsorbent. Preferably, the CO₂-containingstream may be contacted by passing the CO₂-containing stream through theCO₂ adsorbent, for example, with a fixed-bed column. For example, insome embodiments, the CO₂-containing stream is contacted by passing theCO₂-containing stream through the CO₂ adsorbent present in a fixed-bedcolumn. Accordingly, the CO₂-containing stream may have a pressure inthe range of 0.5 to 10 bars, preferably 0.6 to 8 bars, preferably 0.7 to6 bars, preferably 0.8 to 4 bars, preferably 0.9 to 2 bars, preferablyabout 1 bar. The CO₂-containing stream may have a temperature in therange of −20 to 100° C., preferably −10 to 80° C., preferably 0 to 60°C., preferably 10 to 40° C., preferably 20 to 30° C., preferably about25° C. The CO₂-containing stream may have a flow rate in the range of0.01 L/min to 100,000 L/min, preferably 0.1 L/min to 50,000 L/min,preferably 1.0 L/min to 10,000 L/min, preferably 10 L/min to 5,000L/min, preferably 100 L/min to 1,000 L/min, preferably about 500 L/min.The CO₂-containing stream may have an hourly space velocity in the rangeof 0.1 to 10,000 hr⁻¹, preferably 1.0 to 1,000 hr⁻¹, preferably 10 to800 hr⁻¹ preferably 50 to 500 hr⁻¹.

In one embodiment, the CO₂ adsorbent is thermally treated with an inertgas, e.g. nitrogen, helium, and/or argon, at a temperature in the rangeof 300 to 500° C., preferably 350 to 450° C., preferably about 400° C.,for 1 to 6 hours, preferably about 2 to 3 hours, prior to contacting theCO₂-containing stream with the CO₂ adsorbent. This optionally preferredstep of thermal treatment of the CO₂ adsorbent may evaporate residualwater and/or decompose organic compounds present in the CO₂ adsorbent,and thus may open pores and increase a specific surface area of the CO₂adsorbent.

In a preferred embodiment, the CO₂ adsorbent is degassed in asub-atmospheric pressure of 0.05 to 0.9 atm, preferably 0.1 to 0.5 atm,prior to contacting the CO₂-containing stream with the CO₂ adsorbent.The CO₂ adsorbent may be degassed at a temperature in the range of 10 to400° C., preferably 50 to 350° C., preferably 100 to 300° C., preferably150 to 250° C., for no more than 24 hours, preferably no more than 12hours, preferably 1 to 6 hours, preferably about 2 to 3 hours, prior tothe contacting. In a preferred embodiment, the CO₂ adsorbent is degassedin different temperature ranges depending on a composition of the CO₂adsorbent. For example, in some embodiments, the CO₂ adsorbent includesmetal organic frameworks (MOFs), wherein the CO₂ adsorbent is degassedat a temperature of up to 250° C., preferably 50 to 220° C., preferably100 to 210° C., preferably 150 to 200° C. Alternatively, in some otherembodiments, the CO₂ adsorbent includes a zeolite and does not includemetal organic frameworks (MOFs), wherein the CO₂ adsorbent is degassedat a temperature of up to 400° C., preferably 50 to 350° C., preferably100 to 300° C., preferably 150 to 250° C.

After the contacting, in a preferred embodiment, the method of capturingCO₂ further involves heating the CO₂ adsorbent to a temperature in therange of 50 to 250° C., preferably 50 to 250° C., preferably 80 to 200°C., preferably 100 to 150° C., wherein a retained CO₂, i.e. CO₂ that isadsorbed onto the CO₂ adsorbent, is desorbed and is further collected asa CO₂ stream. Alternatively, the retained CO₂ may be desorbed bylowering an atmospheric pressure of the CO₂ adsorbent to a pressure inthe range of 0.05 to 0.9 atm, preferably 0.1 to 0.5 atm. Yet in anotherembodiment, the retained CO₂ may be desorbed by flushing steam to causethe CO₂ adsorbent to desorb the retained CO₂. According to thisembodiment, the CO₂ adsorbent may further be flushed by an air stream toremove residual steam from the CO₂ adsorbent.

The CO₂ stream includes CO₂ and may further include one or more gaseoussubstances including but not limited to, nitrogen, oxygen, argon,helium, water vapor, hydrogen, carbon monoxide, methane, ethane,hydrogen sulfide, nitrogen oxides (i.e. nitric oxide, nitrous oxide,nitrogen dioxide), or sulfur dioxide. Preferably, a volumetric ratio ofCO₂ in the CO₂ stream to the one or more gaseous substances of the CO₂stream may vary in the range of 200:1 to 1:1, preferably 150:1 to 5:1,preferably 100:1 to 10:1, preferably 95:1 to 15:1, preferably 90:1 to20:1, preferably 85:1 to 25:1, preferably 80:1 to 30:1, preferably 75:1to 35:1, preferably 70:1 to 40:1.

The CO₂ stream, which is preferably a substantially pure carbon dioxidestream, may further be injected into a geological formation, or the CO₂stream may be captured by other means known to those skilled in the art.The CO₂ stream may also be utilized in supercritical extraction systems.Alternatively, the CO₂ stream may be utilized to dilute gaseous streams,or may be utilized in processes where a low/medium/high pressure CO₂stream is demanded. For example, in one embodiment, the CO₂ stream maybe mixed with a fuel or an oxygen stream before feeding into acombustor. In an alternative embodiment, the CO₂ stream may be mixedwith an enriched-oxygen stream prior to delivering to an ion transportmembrane.

The CO₂ adsorbent includes an adsorbent matrix comprising a zeoliteand/or a metal organic framework (MOF). Preferably, the adsorbent matrixincludes both the zeolite and the MOF, even though in some embodimentsthe adsorbent matrix may only have the zeolite or the MOF.

The adsorbent matrix may preferably include one or more metal organicframeworks (MOF) selected from Mg-MOF-74, MIL-100(Fe), MOF-5, MOF-177,MOF-199, or MOF-210. MOFs are highly porous, crystalline materials thatare constructed from metal oxide and rigid organic molecular buildingblocks. The MOFs that are utilized herein may have a BET surface area ofup to 10,000 m²/g, preferably in the range of 1,000 to 5,000 m²/g, morepreferably 1,500 to 2,500 m²/g. Also, the MOFs may have a specific porevolume of up to 3.0 cm³/g, preferably in the range of 0.1 to 1.5 cm³/g,more preferably 0.5 to 1.0 cm³/g. A pore structure of the MOF may bemodified at the molecular level by altering pore diameters,polarizability, and hydrophobicity of the MOF. Said modifications mayresult in an increase in a CO₂ adsorption capacity of the CO₂ adsorbent.In some alternative embodiments, the metal-organic framework includes[Me₂(4,4′-bipyridine)₃(NO₃)₄], wherein Me represents any one of Co, Ni,and Zn. The MOF may also include [Me₂(1,4-benzenedicarboxylate anion)₂],wherein Me represents any one of Cu and Zn. Additionally, the MOF mayinclude [Fe₂(trans-4,4′-azopyridine)₄(NCS)₄]. Alternatively, themetal-organic framework utilized in the CO₂ adsorbent may have a generalformula of Me_(x)O(RC)_(y), wherein Me is a transition metal, preferablyZn, Ni, Co, or Cu, and wherein each of x and y are independently apositive integer in the range of 1 to 8, preferably 3 to 5. Also, (RC)in the general formula represents any one of an aromatic carboxylate, anaromatic dicarboxylate, and anionic derivatives thereof including, forexample, 1,4-benzenedicarboxylate anion,2-bromo-1,4-benzenedicarboxylate anion, 2-amino-1,4-benzenedicarboxylateanion, 2,5-propyl-1,4-benzenedicarboxylate anion,2,5-pentyl-1,4-benzenedicarboxylate anion,cyclobutene-1,4-benzenedicarboxylate anion, 1,4-naphthalenedicarboxylateanion, 2,6-naphthalenedicarboxylate anion, 4,4′-biphenyldicarboxylateanion, 4,5,9,10-tetrahydropyrene-2,7-dicarboxylate anion,pyrene-2,7-dicarboxylate anion, and 4,4′-terphenyldicarboxylate anion.The MOFs are preferably stable during operating conditions of capturingCO₂, in other words the MOFs preferably maintain a porous framework evenwhen guest molecules are absent.

The adsorbent matrix may include a zeolite, in addition to or in lieu ofthe metal organic framework. The zeolite may preferably be selected fromthe group consisting of zeolite 13X, MCM-41, ZSM-5, ZSM-8, ZSM-11,ZSM-12, ZSM-18, ZSM-23, ZSM-35 and ZSM-39. In a preferred embodiment,the zeolite of the CO₂ adsorbent is zeolite 13X. Preferably, the zeoliteof the CO₂ adsorbent may have a SiO₂/Al₂O₃ molar ratio in the range of23-10,000, or preferably 100-2,000, or preferably 500-1,500.

Water molecules may also be present inside channels, channelintersections, and/or cage structures of the zeolite, however, thermallytreating and/or degassing the CO₂ adsorbent may preferably remove atleast 99 wt %, preferably at least 99.5 wt % of water, relative to thetotal weight of water present in the zeolite before thermally treatingand/or degassing the CO₂ adsorbent.

The zeolite of the CO₂ adsorbent may be a 4-membered ring zeolite, a6-membered ring zeolite, a 10-membered ring zeolite, and/or a12-membered ring zeolite. Also, the zeolite may have a natroliteframework (e.g. gonnardite, natrolite, mesolite, paranatrolite,scolecite, and tetranatrolite), an edingtonite framework (e.g.edingtonite and kalborsite), a thomsonite framework, an analcimeframework (e.g. analcime, leucite, pollucite, and wairakite), aphillipsite framework (e.g. harmotome), a gismondine framework (e.g.amicite, gismondine, garronite, and gobbinsite), a chabazite framework(e.g. chabazite-series, herschelite, willhendersonite, and SSZ-13), afaujasite framework (e.g. faujasite-series, Linde type X, and Linde typeY), a mordenite framework (e.g. maricopaite and mordenite), a heulanditeframework (e.g. clinoptilolite and heulandite-series), a stilbiteframework (e.g. barrerite, stellerite, and stilbite-series), abrewsterite framework, or a cowlesite framework.

In some embodiments, the zeolite of the CO₂ adsorbent includesmicro-pores (i.e. pores with an average pore diameter of less than 2 nm,preferably in the range of 4-12 Å, more preferably 5-10 Å, even morepreferably 6-8 Å) with a micro-pore specific surface area in the rangeof 10-50 m²/g preferably 20-40 m²/g and a micro-pore specific porevolume in the range of 0.01-0.3 cm³/g, preferably 0.02-0.2 cm³/g, morepreferably 0.05-0.1 cm³/g. The zeolite of the CO₂ adsorbent may furtherinclude meso-pores (i.e. pores with an average pore diameter in therange of 2-50 nm, preferably 5-20 nm) with a meso-pore specific porevolume in the range of 0.01-0.15 cm³/g, preferably 0.05-0.12 cm³/g, morepreferably 0.08-0.1 cm³/g, and a meso-pore specific surface area in therange of 20-80 m²/g, preferably 30-70 m²/g.

In one embodiment, at least one transition metal may also be presentinside channels, channel intersections, and/or cage structures of thezeolite. The at least one transition metal may be selected from theelements of groups 6 to 12 of the periodic table, preferably includingCu, Ag, Au, V, Cr, Mo, W, Mn, Pt, Pd, Fe, Ni, Zn, Ga, and Re. Saidtransition metals may also be present in oxide forms in the zeolite. Inone embodiment, the zeolite of the CO₂ adsorbent may be in a form of apillared zeolite, wherein pillars (e.g. silica pillars) are locatedbetween two adjacent layers in the zeolite.

In one embodiment, a selectivity of the zeolite with respect to carbondioxide relative to the gaseous substances, which may be present in theCO₂-containing stream, is at least 50%, preferably at least 60%,preferably at least 70%, preferably at least 80%, preferably at least90%, preferably at least 95%, preferably at least 98%, preferably atleast 99%. The term “selectivity” as used herein refers to a capabilityof a zeolite to separate carbon dioxide in the presence of the gaseoussubstances in the CO₂-containing stream. For example, the phraseselectivity of the zeolite with respect to carbon dioxide is at least90%” refers to an embodiment, wherein 90% by mole of the totalsubstances that are adsorbed onto the CO₂ adsorbent is carbon dioxide.

In a preferred embodiment, the adsorbent matrix includes the zeolite andthe MOF, wherein a weight ratio of the zeolite to the MOF is in therange of 10:1 to 1:10, preferably 8:1 to 1:8, preferably 5:1 to 1:6,preferably 3:1 to 1:5, preferably 2:1 to 1:4, preferably 1:1 to 1:3,preferably 1:1.5 to 1:2.

Depending on the weight ratio of the zeolite to the MOF, a thermalconductivity of the adsorbent matrix may be in the range of 0.1 to 1.0W/m·K, or 0.2 to 0.5 W/m·K, or 0.25 to 0.4 W/m·K. Said thermalconductivity ranges may be relatively low particularly for CO₂ capturingapplications. Therefore, it may be preferable to incorporate a carbonmaterial into the adsorbent matrix to increase the thermal conductivityof the CO₂ adsorbent. Exemplary carbon materials may include, but arenot limited to carbon nanotubes, graphite flakes, activated carbonparticles, graphene sheets, carbon fibers, and fullerenes. The carbonmaterials may increase an overall thermal conductivity of the CO₂adsorbent by up to 500%, preferably up to 400%, preferably up to 300%,preferably up to 200%, preferably up to 100%, preferably about 10% to80%, more preferably about 20% to 60%.

The CO₂ adsorbent further includes carbon nanotubes (CNTs) that aredispersed within the adsorbent matrix. A weight percent of the carbonnanotubes in the CO₂ adsorbent is in the range of 0.01 wt % to 5.0 wt %,preferably 0.02 wt % to 4.0 wt %, preferably 0.03 wt % to 3.0 wt %,preferably 0.04 wt % to 2.0 wt %, preferably 0.05 wt % to 1.8 wt %,preferably 0.1 wt % to 1.5 wt %, relative to the total weight of the CO₂adsorbent.

In one embodiment, the carbon nanotubes are single-walled carbonnanotubes, with an average diameter in the range of 0.5 to 5 nm,preferably 1 to 4 nm, more preferably about 1.5 to 3 nm, and an aspectratio (i.e. a ratio of length-to-diameter) of greater than or equal toabout 500, preferably greater than or equal to about 1,000, morepreferably greater than or equal to about 10,000. The single-walledcarbon nanotubes may be closed structures having hemispherical caps ateach end of respective tubes, or they may have a single open end or bothopen ends.

In a preferred embodiment, the carbon nanotubes are multi-walled carbonnanotubes, with an average diameter within the range of 5 to 40 nm,preferably 10 to 20 nm, more preferably about 12 to 18 nm, and an aspectratio of greater than or equal to about 100, preferably greater than orequal to about 500, more preferably greater than or equal to about1,000. The multi-walled carbon nanotubes may be closed structures havinghemispherical caps at each end of respective tubes, or they may have asingle open end or both open ends.

In some embodiments, the carbon nanotubes are dispersed in the adsorbentmatrix without forming chemical bonds, e.g., covalent and/or ionicbonds, with the adsorbent matrix. Accordingly, pristine carbon nanotubesare preferably utilized in the process of fabricating the CO₂ adsorbent,without being treated with an acid (e.g. nitric acid). Therefore,oxidized functionalities (e.g. carboxylic acid functional groups) arepreferably not present on the carbon nanotubes. The carbon nanotubes maybe dispersed in the adsorbent matrix by known methods in the art suchas, for example, sonication, ultra-sonication, centrifugation,roll-milling, etc. In view of that, in a preferred embodiment, thecarbon nanotubes are homogenously dispersed in the adsorbent matrix. Theterm “carbon nanotubes are homogenously dispersed in the adsorbentmatrix” as used herein refers to an embodiment, wherein a volumetricconcentration of carbon nanotubes of any cubic-micron (1 μm³) of thematrix is no more than 10%, preferably no more than 5%, preferably nomore than 1% of the volumetric concentration of carbon nanotubes ofanother cubic-micron (1 μm³) of the matrix.

In another embodiment, the CO₂ adsorbent further includes exfoliatedgraphite flakes to increase the thermal conductivity of the CO₂adsorbent. The exfoliated graphite flakes may be obtained by mechanicalmethods known in the art, e.g. roll-milling, or microwave expansion. Theexfoliated graphite flakes may preferably not be functionalized, andthus the graphite flakes do not form chemical bonds with the adsorbentmatrix. The exfoliated graphite flakes may be present in an amount of nomore than 1.0% by volume, preferably no more than 0.5% by volume,relative to the total volume of the CO₂ adsorbent. The presence of theexfoliated graphite flakes may increase the thermal conductivity of theCO₂ adsorbent by at least 50%, preferably by about 80% to about 150%,preferably by about 100% to about 120%, which may be obtained frompercolation of the exfoliated graphite flakes.

In some embodiments, the thermal conductivity of the CO₂ adsorbent is inthe range from about 0.001 to about 50 W/m·K, preferably from about0.005 to about 40 W/m·K, preferably from about 0.01 to about 30 W/m·K,preferably from about 0.05 to about 20 W/m·K, preferably from about 0.1to about 10 W/m·K.

A CO₂ adsorption capacity of the CO₂ adsorbent may be improved by addingcarbon nanotubes, and preferably exfoliated graphite flakes.Accordingly, in some embodiments, the CO₂ adsorbent has 0.01 wt % to 5.0wt %, preferably 0.1 wt % to 1.5 wt % of carbon nanotubes, wherein a CO₂adsorption capacity of the CO₂ adsorbent is in the range of 0.5 to 20mmol/g (millimole CO₂ per one gram of the CO₂ adsorbent), preferably 1.0to 18 mmol/g, preferably 2.0 to 15 mmol/g, preferably 3.0 to 12 mmol/g,preferably 4.0 to 10 mmol/g, at a temperature in the range of 10 to 40°C., preferably 15 to 30° C., preferably 22 to 28° C. In anotherembodiment, the CO₂ adsorption capacity of the CO₂ adsorbent with carbonnanotubes is up to 20%, preferably 10% to 20%, preferably 12% to 18%,higher than the CO₂ adsorption capacity of a pristine adsorbent thatdoes not include carbon nanotubes.

In addition, a CO₂ mass diffusivity (i.e. a coefficient of moleculardiffusion of CO₂ through the CO₂ adsorbent) of the CO₂ adsorbent mayimprove by adding carbon nanotubes. For example, in one embodiment, theCO₂ mass diffusivity of the CO₂ adsorbent may be at least 50%,preferably at least 100%, preferably 150% to 400%, preferably 200% to300% higher than the CO₂ mass diffusivity of a pristine adsorbent thatdoes not include carbon nanotubes. An increase in the CO₂ massdiffusivity may speed up the adsorption/desorption processes of CO₂. ACO₂ mass diffusivity of the CO₂ adsorbent may be in the range of 10⁻⁹ to5.0×10⁻⁵ cm²/s, preferably 10⁻⁹ to 5.0×10⁻⁵ cm²/s, preferably 5×10⁻⁸ to6.0×10⁻⁵ cm²/s, preferably 10⁻⁸ to 8.0×10⁻⁵ cm²/s, preferably 5×10⁻⁷ to10⁻⁶ cm²/s, at a temperature in the range of 10 to 40° C., preferably 15to 30° C., preferably 22 to 28° C.

In one embodiment, the CO₂ adsorbent further includes an organic bindersuch as melamine and/or hydroxyethyl-cellulose to improve the CO₂ massdiffusivity of the CO₂ adsorbent. Additionally, the organic binders mayenhance a binding strength between components of the CO₂ adsorbent, i.e.the MOF, the zeolite, and the carbon nanotubes.

In some embodiments, the CO₂ adsorbent further includes one or moreactive compounds to enhance the CO₂ adsorption capacity of the CO₂adsorbent. Exemplary active compounds may include, but are not limitedto desiccant particles, activated alumina particles, molecular sieves,aluminophosphate particles, silicoaluminophosphate particles, ionexchanged zeolite particles, faujasite particles, clinoptiloliteparticles, mordenite particles, metal-exchanged silico-aluminophosphateparticles, an aromatic cross-linked poly styrenic matrix, a brominatedaromatic matrix, a methacrylic ester copolymer, carbon fibers, a metalsalt adsorbent, a perchlorate, an oxalate, an alkaline earth metalparticle, a metal oxide, a chemisorbent, an amine, an organometalliccompound, or combinations thereof. In some other embodiments, the CO₂adsorbent further includes one or more inactive compounds including, forexample, clay, silica, a ceramic, an adhesive, or combinations thereof.

In some embodiments, the CO₂ adsorbent preferably includes micro-pores(i.e. pores with an average pore diameter of less than 2 nm, preferablyin the range of 4-12 Å, more preferably 5-10 Å, even more preferably 6-8Å) with a micro-pore specific pore volume in the range of 0.01-0.15cm³/g, preferably 0.05-0.12 cm³/g, more preferably 0.08-0.1 cm³/g, and amicro-pore specific surface area in the range of 10-500 m²/g, preferably100-400 m²/g, more preferably 200-350 m²/g. The CO₂ adsorbent mayfurther include meso-pores (i.e. pores with an average pore diameter inthe range of 2-50 nm, preferably 5-20 nm) with a meso-pore specific porevolume in the range of 0.1-0.5 cm³/g, preferably 0.15-0.45 cm³/g, morepreferably 0.2-0.4 cm³/g, and a meso-pore specific surface area in therange of 200-800 m²/g, preferably 300-700 m²/g. Also, the CO₂ adsorbentmay further include macro-pores (i.e. pores with an average porediameter of greater than 50 nm, preferably in the range of 40 to 100 nm,preferably 50 to 90 nm) with a macro-pore specific pore volume in therange of 0.2-1.0 cm³/g, preferably 0.5-0.8 cm³/g, and a macro-porespecific surface area in the range of 500-1,200 m²/g, preferably600-1,000 m²/g, more preferably 700-900 m²/g. In view of that, the CO₂adsorbent may preferably have an average pore size in the range of 1 to100 nm, preferably 5 to 80 nm, preferably 10 to 70 nm.

According to a second aspect, the present disclosure relates to a CO₂adsorbent that includes an adsorbent matrix comprising MIL-100(Fe) andcarbon nanotubes, wherein the carbon nanotubes are dispersed in theadsorbent matrix without forming chemical bonds with the adsorbentmatrix.

Preferably, the adsorbent matrix only includes MIL-100(Fe). Yet in somealternative embodiments, the adsorbent matrix includes MIL-100(Fe) andone or more zeolites selected from zeolite 13X, MCM-41, ZSM-5, ZSM-8,ZSM-11, ZSM-12, ZSM-18, ZSM-23, ZSM-35 and ZSM-39. Accordingly, a weightratio of the zeolite(s) to the MIL-100(Fe) is in the range of 1:1 to1:10, preferably 1:2 to 1:9, preferably 1:3 to 1:8, preferably 1:4 to1:6. In a preferred embodiment, a weight percent of the carbon nanotubesin the CO₂ adsorbent is in the range of 0.01 wt % to 2.0 wt %,preferably 0.02 wt % to 1.5 wt %, preferably 0.03 wt % to 1.0 wt %,preferably 0.04 wt % to 0.5 wt %, preferably 0.05 wt % to 0.4 wt %,preferably 0.08 wt % to 0.2 wt %, preferably about 0.1 wt %, relative tothe total weight of the CO₂ adsorbent.

Depending on the composition, the CO₂ adsorbent may exhibit differentthe, mal conductivities, different CO₂ mass diffusivities, and differentCO₂ adsorption capacity. For example, in some preferred embodiments, theadsorbent matrix consists of MIL-100(Fe) and carbon nanotubes, whereinthe carbon nanotubes are physical dispersed without forming chemicalbonds with the MIL-100(Fe), and wherein a weight percent of the carbonnanotubes varies in the range between 0.05 wt % to 0.4 wt %, preferably0.08 wt % to 0.2 wt %, preferably about 0.1 wt %, relative to the totalweight of the CO₂ adsorbent. In view of that, the CO₂ adsorptioncapacity of the CO₂ adsorbent may preferably be in the range of 0.5 to10 mmol/g, preferably 1.0 to 9.0 mmol/g, at a temperature in the rangeof 10 to 40° C., preferably 15 to 30° C., preferably 22 to 28° C.Furthermore, the CO₂ mass diffusivity of the CO₂ adsorbent may be in therange of 10⁻⁹ to 5.0×10⁻⁵ cm²/s, preferably 10 ⁻⁹ to 5.0×10⁻⁵ cm²/s,preferably 5×10⁻⁸ to 6.0×10⁻⁵ cm²/s, preferably 10⁻⁸ to 8.0×10⁻⁵ cm²/s,preferably 5×10⁻⁷ to 10⁻⁶ cm²/s, at a temperature in the range of 10 to40° C., preferably 15 to 30° C., preferably 22 to 28° C. Also, thethermal conductivity of the CO₂ adsorbent is in the range from about0.001 to about 50 W/m·K, preferably from about 0.005 to about 40 W/m·K,preferably from about 0.01 to about 30 W/m·K, preferably from about 0.05to about 20 W/m·K, preferably from about 0.1 to about 10 W/m·K.

Referring to FIG. 1, another aspect of the present disclosure relates toa CO₂ capturing system 100, and the method may involve capturing CO₂with the system. In some embodiments, the CO₂ capturing system 100includes an adsorbent bed 102, and a first supplier 104 that is fluidlyconnected to the adsorbent bed 102 via a first supplier line 108 and afeed line 110. Preferably, the first supplier 104 supplies aCO₂-containing stream to the adsorbent bed 102. In another embodiment, asecond supplier 106 is fluidly connected to the adsorbent bed 102 via asecond supplier line 109 and the feed line 110. Preferably, the secondsupplier 106 supplies a diluent gaseous stream,e.g. nitrogen, helium,argon, etc. to be mixed with the CO₂-containing stream prior to feedingthe CO₂-containing stream to the adsorbent bed 102 via the feed line110. The adsorbent bed may preferably be a horizontally-oriented (asshown in FIG. 1) or a vertically-oriented (not shown) vessel packed withthe CO₂ adsorbent.

In some embodiments, the CO₂ capturing system 100 further includes afirst actuator 112 and a processing unit 124 that communicates with acompositional analyzer 123, which is disposed in the adsorption bed 102,and/or a mass spectrometer 122, which is fluidly connected to a CO₂ line126 downstream of the adsorbent bed. The CO₂ capturing system 100further includes a second actuator 114 that communicates with thecompositional analyzer 123 and/or the mass spectrometer 122 via theprocessing unit 124. Accordingly, changes in the composition of aCO₂-depleted stream or a CO₂ stream that flow inside the CO₂ line 126,and also changes in the composition of a gaseous stream inside theadsorbent bed 102 is preferably instantaneously monitored. Therefore,any variations in the composition of the CO₂-depleted stream or the CO₂stream may be adjusted by regulating a flow rate of the CO₂-containingstream with the first actuator 112. Similarly, any variations in thecomposition of the gaseous stream may be adjusted by regulating a flowrate of the diluent gaseous stream with the second actuator 114. The CO₂capturing system 100 may further include a flowmeter 118 disposed in thefeed line 110, a bypass line 120, and a plurality of valves 116 disposedin the feed line 110, the CO₂ line 126, and the bypass line 120. Saidlines, valves, actuators, suppliers, the flowmeter, the processing unit,the mass spectrometer, and the adsorbent bed utilized in the CO₂capturing system are not meant to be limiting, and various lines,valves, actuators, suppliers, flowmeters, processing units, massspectrometers, and adsorbent beds may also be used.

One aspect of the present disclosure relates to a method of fabricatingthe CO₂ adsorbent, which is described in the second aspect. The methodmay involve two or more steps, wherein MIL-100(Fe) is produced in afirst step, followed by forming the CO₂ adsorbent in a second step.According to the first step, a predetermined amount of a ferric nitrate,preferably a hydrated ferric nitrate (e.g. Fe(NO₃)₃.xH₂O, with x in therange of 1 to 12, preferably 8 to 10) is mixed with water, preferablyde-ionized water, and an aromatic carboxylate (e.g. benzenetricarboxylicacid) to form a first mixture. The first mixture is hydrothermallytreated in an autoclave at a temperature in the range of 140 to 220° C.,preferably 160 to 200° C., and a pressure in the range of 1 to 6 bars,preferably 2 to 4 bars, for no more than 24 hours, preferably 10 to 18hours, preferably about 15 hours, wherein the MIL-100(Fe) and/orMIL-100(Fe) nuclei are formed in the autoclave. The MIL-100(Fe) and/orMIL-100(Fe) nuclei may further be separated by centrifugation (or otherknown methods in the art), and may be washed with water and/or anorganic solvent, e.g. acetone, methanol, or toluene. According to thesecond step, a predetermined amount of the MIL-100(Fe) and/orMIL-100(Fe) nuclei is mixed with the ferric nitrate, preferably ahydrated ferric nitrate (e.g. Fe(NO₃)₃.xH₂O, with x in the range of 1 to12, preferably 8 to 10), water, preferably de-ionized water, thearomatic carboxylate (e.g. benzenetricarboxylic acid), and carbonnanotubes to form a second mixture. The second mixture may becentrifuged and/or sonicated for 2 to 12 hours, preferably 4 to 10hours, and further be hydrothermally treated in an autoclave at atemperature in the range of 140 to 220° C., preferably 160 to 200° C.,and a pressure in the range of 1 to 6 bars, preferably 2 to 4 bars, forno more than 24 hours, preferably 10 to 18 hours, preferably about 15hours, wherein the CO₂ adsorbent is formed that includes MIL-100(Fe) andcarbon nanotubes that are dispersed therein. The CO₂ adsorbent mayfurther be separated by centrifugation (or other known methods in theart), and may be washed with water and/or an organic solvent, e.g.acetone, methanol, or toluene. In some embodiments, exfoliated graphiteflakes are also mixed with the second mixture.

The examples below are intended to further illustrate protocols for theCO₂ adsorbents and the method of capturing CO₂ with the CO₂ adsorbents,and are not intended to limit the scope of the claims.

EXAMPLE 1

The present disclosure considers physical incorporation of carbonnanotubes (CNTs) in different adsorbent materials (such as carbon-basedadsorbents, zeolites, and metal organic frameworks (MOFs)) to provide aCO₂ adsorbent with a large CO₂ adsorption capacity. Since CNTs are knownto have very high thermal conductivity (up to 3000 W/m·K), incorporatingthem with adsorbents such as Zeolites and/or MOFs may provide a newmaterial composition with higher thermal conductivity than the pristineadsorbents. The following examples provide characterization of differentCO₂ adsorbents that include zeolite 13X, Mg-MOF-74, and/or MIL-100(Fe)with various amount of carbon nanotubes.

EXAMPLE 2 X-Ray Powder Diffraction Analysis

Powder X-Ray diffraction patterns for MWCNT/Mg-MOF-74 and CNT/13X wereobtained and collected using a Bruker D8-Advance Diffractometer (CuK_(α)λ=1.54056 Å) with an operating power of 30 kV/30 mA. The data wererecorded by the step-counting method (step=0.02°, time=3 s) in the range2θ=3-45° at ambient temperature of 298 K. FIG. 2 represents X-raydiffraction spectra of CO₂ adsorbents having zeolite 13X and variousamounts of carbon nanotubes (i.e. CNT/13X). Also, FIG. 6 representsX-ray diffraction spectra of CO₂ adsorbents having Mg-MOF-74 and variousamounts of carbon nanotubes (i.e. MWCNT/Mg-MOF-74). According to thesefigures, a substantial change is observed in the XRD spectra of the CO₂adsorbents after adding carbon nanotubes. As evident from FIG. 6, theincorporation of CNTs does not result in a noticeable peak shift or adecrease in the crystallinity of the framework, as all thecharacteristic peaks representative of the Mg-MOF-74 structure can alsobe observed in the patterns shown for the CNT/Mg-MOF-74 adsorbents.

EXAMPLE 3 Gas Sorption Measurements

The first step in the physiosorption measurements of CO₂ is the sampledegassing in order to remove any guest molecules within the pores ofeach material. Typically, 50-200 mg of each sample was transferred topre-weighed empty sample cell with a 9 mm diameter. Degassing wasconducted at 150° C. under vacuum for about 17 hours forMWCNT/MIL-100(Fe) adsorbents, 220° C. under vacuum during about 5 hoursfor MWCNT/Mg-MOF-74 adsorbents, and 250° C. under vacuum during 20 hoursfor CNT/13X adsorbents using an Autosorb degasser equipped with a turbomolecular vacuum pump and controlled heat jackets (QuantachromeInstruments, Inc.). The equilibrium adsorption isotherms for CO₂ havebeen measured at 298 K. Accordingly, FIG. 3 represents CO₂ adsorptionisotherms of CO₂ adsorbents having zeolite 13X and various amounts ofcarbon nanotubes, at 298 K. FIG. 7 represents CO₂ adsorption isothermsof CO₂ adsorbents having Mg-MOF-74 and various amounts of carbonnanotubes, at 298 K. Also, FIG. 10 represents CO₂ adsorption isothermsof CO₂ adsorbents having MIL-100(Fe) and various amounts of carbonnanotubes, at 298 K.

EXAMPLE 4 Binary Gas (CO₂+N₂) Breakthrough Experiments

The gas separation capabilities of all the samples were examined using adeveloped dynamic CO₂/N₂ breakthrough setup. The system consists of afixed adsorbent bed column filled with compounds, feed CO₂ and N₂cylinders (for simulating a flue gas). The system included two gasregulators with dual pressure gauges and output control valves, two massflow controllers (one was calibrated for CO₂ flow and the other wascalibrated for N₂), two check valves (to control the flow in onedirection) and a bypass line (for calibrating the mass spectrometer fromthe feed gas mixture). The system also comprised a bourdon absolutepressure, a mass spectrometer (to analyze the output concentration ofeffluent gases from the bed), heater jacket and vacuum pump (fordesorption process to regenerate the adsorbent) and some valves andtubes to control the flow. All pipes and fittings were made of stainlesssteel to keep off corrosion contaminants. All tests have been carried atambient conditions (297 K and 101.3 kPa). The CO₂ inlet partial pressurewas 20% of an inlet CO₂/N₂ mixture (101.3 kPa) for CNT/13X andCNT/Mg-MOF-74 samples, while that was 15% for CNT/MIL-100(Fe).

The CO₂ adsorption of the CO₂ adsorbents are presented by breakthroughcurves of CO₂/N₂ separation as shown in FIG. 4, FIG. 8, and FIG. 11.FIG. 4 represents breakthrough curves of CO₂ adsorbents having zeolite13X and various amounts of carbon nanotubes, at a temperature of 25° C.and a pressure of 1.0 atm, wherein a CO₂-containing stream having CO₂and N2, with a CO₂:N2 volumetric ratio of 1:4, is contacted with the CO₂adsorbents. FIG. 8 represents breakthrough curves of CO₂ adsorbentshaving Mg-MOF-74 and various amounts of carbon nanotubes, at atemperature of 25° C. and a pressure of 1.0 atm, wherein aCO₂-containing stream having CO₂ and N2, with a CO₂:N2 volumetric ratioof 1:4, is contacted with the CO₂ adsorbents. Also, FIG. 11 representsbreakthrough curves of CO₂ adsorbents having MIL-100(Fe) and variousamounts of carbon nanotubes, at a temperature of 25° C. and a pressureof 1.0 atm, wherein a CO₂-containing stream having CO₂ and N2, with aCO₂:N2 volumetric ratio of 1:5.6, is contacted with the CO₂ adsorbents.

In addition, the levels of enhancement in the adsorption uptake andbreakpoint of the CO₂ adsorbents are shown in FIG. 5, FIG. 9, and FIG.12. FIG. 5 represents the CO₂ adsorption capacity (dashed bars) and thebreakpoint onset (solid bars) of CO₂ adsorbents having zeolite 13X andvarious amounts of carbon nanotubes, at a temperature of 25° C. and apressure of 1.0 atm. FIG. 9 represents the CO₂ adsorption capacity(dashed bars) and the breakpoint onset (solid bars) of CO₂ adsorbentshaving Mg-MOF-74 and various amounts of carbon nanotubes, at atemperature of 25° C. and a pressure of 1.0 atm. FIG. 12 represents theCO₂ adsorption capacity (dashed bars) and the breakpoint onset (solidbars) of CO₂ adsorbents having MIL-100(Fe) and various amounts of carbonnanotubes, at a temperature of 25° C. and a pressure of 1.0 atm.

In the above figures, the label “MFC” represents the CO₂ adsorbents withMg-MOF-74 and various amounts of carbon nanotubes. Accordingly, MFC1,MFC2, MFC3, MFC4, MFC5, and MFC6 relate to the 0.1 wt % CNT/Mg-MOF-74adsorbent, the 0.25 wt % CNT/Mg-MOF-74 adsorbent, the 0.5 wt %CNT/Mg-MOF-74 adsorbent, the 0.75 wt % CNT/Mg-MOF-74 adsorbent, the 1 wt% CNT/Mg-MOF-74 adsorbent, and the 1.5 wt % CNT/Mg-MOF-74 adsorbent,respectively. Also, the label “MMC” represents the CO₂ adsorbents withMIL-100(Fe) and various amounts of carbon nanotubes. Accordingly, MMC1,MMC2, and MMC3, relate to the 0.1 wt % CNT/MIL-100(Fe) adsorbent, the0.25 wt % CNT/MIL-100(Fe) adsorbent, and the 0.5 wt % CNT/MIL-100(Fe)adsorbent, respectively.

1-13. (canceled)
 14. A CO₂ adsorbent comprising: an adsorbent matrixcomprising MIL-100(Fe), and carbon nanotubes that are dispersed withinthe adsorbent matrix, wherein the carbon nanotubes are dispersed in theadsorbent matrix without forming chemical bonds with the adsorbentmatrix.
 15. The CO₂ adsorbent of claim 14, wherein a weight percent ofthe carbon nanotubes in the CO₂ adsorbent is in the range of 0.05 wt %to 1.5 wt %, relative to the total weight of the CO₂ adsorbent.
 16. TheCO₂ adsorbent of claim 14, which has a CO₂ adsorption capacity in therange of 0.5 to 20 mmol CO₂ per one gram of the CO₂ adsorbent, at atemperature in the range of 10 to 40° C.
 17. The CO₂ adsorbent of claim14, which has a thermal conductivity of up to 500% higher than a thermalconductivity of a pristine adsorbent that comprises MIL-100(Fe) and doesnot include carbon nanotubes.
 18. The CO₂ adsorbent of claim 14, whereinthe adsorbent matrix further comprises zeolite 13X and/or Mg-MOF-74. 19.The CO₂ adsorbent of claim 14, wherein the carbon nanotubes arehomogenously dispersed in the adsorbent matrix.
 20. The CO₂ adsorbent ofclaim 14, wherein the carbon nanotubes are multi-walled carbonnanotubes.